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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Cu 2 O/CuS Nanocomposites Show Excellent Selectivity and Stability for Formate Generation via Electrochemical Reduction of Carbon Dioxide

Formate is an important value-added chemical that can be produced via electrochemical CO 2 reduction reactions (CO 2 RR). Cu 2 O-based catalysts have previously demonstrated decent activity for formate generation; however, they often suffer from poor electrochemical stability under reductive conditions. Here, in this paper, we report a new Cu 2 O/CuS composite catalyst that simultaneously achieves an excellent faradaic efficiency of 67.6% and a large partial current density of 15.3 mA/cm 2 at –0.9 V vs RHE for formate. Importantly, it maintains an average faradaic efficiency of 62.9% for at least 30 h at the same potential. The catalytic selectivity and stability for formate production outperform other Cu, CuS, and Cu 2 O catalysts.

36 MATERIALS SCIENCE↗
NASA NTRS1985

Performance characterization tests of a 1-kW resistojet using hydrogen, nitrogen and ammonia as propellants

A performance mapping test of a 1 kW radiatively heated resistojet demonstrated high specific impulse and efficiency with hydrogen, nitrogen and ammonia as propellants. The resistojet was based on an unmodified augmentation section of the flight-qualified Rocket Research Company Augmented Catalytic Thruster. Peak specific impulse values of 686.9 sec for hydrogen, 191.6 sec for nitrogen, and 342 sec for ammonia were demonstrated. A maximum specific impulse efficiency of 94.3 percent was demonstrated with hydrogen. Testing covered a thrust range of 27 to 112 mlbf with augmentation powers ranging from 300 to 1000 watts. A total of 83 runs accumulating 25 hours of operation were conducted with the three propellants. Comparison of specific impulse efficiency to other published resistojet performance data showed the radiatively heated resistojet compares favorably to other design concepts.

Miyake, C. I.↗
DOE OSTI2025

Microwave-Driven Nonoxidative and Selective Conversion of Methane to Ethylene over Mn-Based Catalysts

Recent advancements in microwave-driven nonoxidative catalytic synthesis of C 2 H 4 from CH 4 coupling offer a promising, energy-efficient, and eco-friendly alternative to conventional methods, where selective heating under microwave irradiation enables comparable conversions at substantially lower bulk temperatures and shorter reaction times. This study explores the performance of an MnO X -based catalyst supported on CeO 2 and HY zeolite (silica-toalumina ratio = 5.1) for the nonoxidative coupling of CH 4 (NOCM) under microwave irradiation. Inspired by the well-established efficacy of MnO X catalyst in oxidative CH 4 coupling (OCM), their application in NOCM has also shown significant performance. The catalytic system achieved 15% CH 4 conversion and 99% selectivity toward C 2 hydrocarbons and maintained 64% selectivity toward C 2 H 4 surpassing the yields reported in the literature even at higher temperatures (700−1000 °C). Catalyst performance was correlated with measurements by in situ Raman spectroscopy, and additional characterizations were performed using H 2 −temperature programmed reduction , NH 3 −temperature programmed desorption, and BET surface area analysis to understand structural changes during the reactions. These findings suggested that Mn functions as active sites for CH 4 activation in nonoxidative environments while also promoting efficient C−C coupling under microwave irradiation.

Catalysts↗
NASA NTRS1998

An Evaluation of the Vapor Phase Catalytic Ammonia Removal Process for Use in a Mars Transit Vehicle

An experimental program has been developed to evaluate the potential of the Vapor Phase Catalytic Ammonia Reduction (VPCAR) technology for use as a Mars Transit Vehicle water purification system. Design modifications which will be required to ensure proper operation of the VPCAR system in reduced gravity are also evaluated. The VPCAR system is an integrated wastewater treatment technology that combines a distillation process with high temperature catalytic oxidation. The distillation portion of the system utilizes a vapor compression distillation process to provide an energy efficient phase change separation. This portion of the system removes any inorganic salts and large molecular weight, organic contaminates, i.e., non-volatile, from the product water stream and concentrates these contaminates into a byproduct stream. To oxidize the volatile organic compounds and ammonia, a vapor phase, high temperature catalytic oxidizer is used. This catalytic system converts these compounds along with the aqueous product into CO2, H2O, and N2O. A secondary catalytic bed can then be used to reduce the N2O to nitrogen and oxygen (although not evaluated in this study). This paper describes the design specification of the VPCAR process, the relative benefits of its utilization in a Mars Transit Vehicle, and the design modification which will be required to ensure its proper operation in reduced gravity. In addition, the results of an experimental evaluation of the processors is presented. This evaluation presents the processors performance based upon product water purity, water recovery rates, and power.

Flynn, Michael↗
DOE OSTI2020

Substrate–Support Interactions Mediate Hydrogenation of Phenolic Compounds by Pd/CeO 2 Nanorods

Ceria-supported palladium (Pd/CeO 2 ) has spawned significant attention in recent years due to its ability to catalyze selective hydrogenation of phenolic compounds to cyclohexanones and cyclohexanols at a mild temperature and pressure. However, the mechanistic basis by which ceria enhances catalytic conversion is still unclear. Here, we use the increase in the 13 C transverse relaxation rate upon the addition of nanoparticles (NPs) ( 13 C ΔR 2 ) to investigate the adsorption of phenolic compounds on the surface of the Pd/CeO 2 catalyst by solution NMR. We show that hydroxyphenols adsorb on the support more efficiently than underivatized phenol and methoxyphenols and that phenol derivatives with an oxygen atom at position 2 (i.e., 2-hydroxyphenol and 2-methoxyphenol) form very stable interactions with the Pd site of Pd/CeO 2 . An analysis of the kinetics of hydrogenation revealed that catalytic conversion is linearly correlated with the ability of the substrate to form interactions with the CeO 2 support and is inhibited by the formation of stable substrate–Pd adducts. Our data suggest that CeO 2 –substrate interactions mediate phenol hydrogenation more efficiently than Pd–substrate interactions and explain the exceptional catalytic performance reported for Pd/CeO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Optimizing Microenvironment of Asymmetric N,S-Coordinated Single-Atom Fe via Axial Fifth Coordination toward Efficient Oxygen Electroreduction

We report single-atom catalysts (SACs) are attractive candidates for oxygen reduction reaction (ORR). The catalytic performances of SACs are mainly determined by the surrounding microenvironment of single metal sites. Microenvironment engineering of SACs and understanding of the structure–activity relation-ship is critical, which remains challenging. Herein, a self-sacrificing strategy is developed to synthesize asymmetric N,S-coordinated single-atom Fe with axial fifth hydroxy (OH) coordination (Fe-N 3 S 1 OH) embedded in N,S codoped porous carbon nanospheres (Fe-N/S-C). Such unique penta-coordination microenvironment is determined by cutting-edge techonologies aiding of systematic simulations. The as-obtained Fe-;N/S-C exhibits superior catalytic ORR activity, and showcases a half-wave potential of 0.882 V surpassing the benchmark Pt/C. Moreover, theoretical calculations confirmed the axial OH in Fe-N 3 S 1 OH can optimize 3d orbitals of Fe center to strengthen O 2 adsorption and enhance O 2 activation on Fe site, thus reducing the ORR barrier and accelerating ORR dynamics. Furthermore, Fe-N/S-C containing H 2 -O 2 fuel cell performs a high peak power density of 512 mW cm -2 , and Fe-N/S-C based Zn-air batteries show the peak power density of 203 and 49 mW cm -2 in liquid and flexible all-solid-state configurations, respectively. This study offers a new platform for fundamentally understand the axial fifth coordination in asymmetrical planar single-atom metal sites for electrocatalysis.

microenvironment↗
DOE OSTI2025

Multifunctional Catalysts for the Tandem Reactions of Oxygenates

Industrially-relevant catalytic reactions rarely consist of a simple sequence of elementary steps. Moreover, kinetic coupling of multiple reactions on a catalyst surface is highly desired for process intensification and improved energy efficiency for large scale chemical transformations. The shifting landscape of hydrocarbon chemical feedstocks in the US also motivates research on the selective conversion of more complex molecules. One desirable type of catalytic reaction is the reduction of carboxylic acids that are produced from biomass feedstocks to their corresponding alcohols. The proposed research explores the fundamental importance of hydrogen spillover on a multifunctional catalyst for carboxylic acid reduction with H 2 composed of metal particles coupled to metal oxide particles. Recent work has demonstrated the excellent performance of supported tungsten oxide clusters for carboxylic acid reduction, but only after they are promoted with a late transition metal such as palladium. Elucidating the active state of the catalyst and the associated reaction mechanism for acid reduction on that active state are the overall goals of the proposed project and successful completion will enable future design of efficient multifunctional catalysts. The critically important role of the metal promoter is hypothesized to be its ability to dissociate H2 and spillover atomic H to the support. Although hydrogen spillover is a well-recognized phenomenon in catalysis, its role in both catalyst activation and catalytic turnover are still unresolved. The study combined materials synthesis, characterization, reactivity testing, and molecular simulations, to explore the effect of hydrogen chemical potential on the formation of the active catalytic sites and on the steady state catalytic reduction of carboxylic acid. Varying the hydrogen chemical potential through modification of the gas conditions, support composition, and metal loading to modulated the structure and catalytic performance of the reducible metal oxide. Dual function catalysts containing supported Pd and WO x species co-located on a non-reducible carrier (silica) and a reducible carrier (titania) were synthesized and characterized by electron microscopy, temperature-programmed reduction, and chemisorption. Spectroscopic methods such as X-ray absorption and UV-vis were also used to evaluate the catalysts, which were used in the reduction of propionic acid to aldehyde and alcohol. Quantum chemical calculations, including ab initio phase diagrams provided molecular insights into the H spillover phenomenon.

09 BIOMASS FUELS↗
DOE OSTI2020

Predicting metal–metal interactions. I. The influence of strain on nanoparticle and metal adlayer stabilities

Strain-engineering of bimetallic nanomaterials is an important design strategy for developing new catalysts. In this paper, we introduce an approach for including strain effects into a recently introduced, density functional theory (DFT)-based alloy stability model. The model predicts adsorption site stabilities in nanoparticles and connects these site stabilities with catalytic reactivity and selectivity. Strain-based dependencies will increase the model’s accuracy for nanoparticles affected by finite-size effects. In addition to the stability of small nanoparticles, strain also influences the heat of adsorption of epitaxially grown metal-on-metal adlayers. In this respect, we successfully benchmark the strain-including alloy stability model with previous experimentally determined trends in the heats of adsorption of Au and Cu adlayers on Pt (111). For these systems, our model predicts stronger bimetallic interactions in the first monolayer than monometallic interactions in the second monolayer. We explicitly quantify the interplay between destabilizing strain effects and the energy gained by forming new metal–metal bonds. While tensile strain in the first Cu monolayer significantly destabilizes the adsorption strength, compressive strain in the first Au monolayer has a minimal impact on the heat of adsorption. Hence, this study introduces and, by comparison with previous experiments, validates an efficient DFT-based approach for strain-engineering the stability, and, in turn, the catalytic performance, of active sites in bimetallic alloys with atomic level resolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Hydroxyls on CeO 2 Support Promoting CuO/CeO 2 Catalyst for Efficient CO Oxidation and NO Reduction by CO

Transition metal catalysts, such as copper oxide, are more attractive alternatives to noble metal catalysts for emission control due to their higher abundance, lower cost, and excellent catalytic activity. Here, in this study, we report the preparation and application of a novel CuO/CeO 2 catalyst using a hydroxyl-rich Ce(OH) x support for CO oxidation and NO reduction by CO. Compared to the catalyst prepared from a regular CeO 2 support, the new CuO/CeO 2 catalyst prepared from the OH-rich Ce(OH) x (CuO/CeO 2 –OH) showed significantly higher catalytic activity under different testing conditions. The effect of OH species in the CeO 2 support on the catalytic performance and physicochemical properties of the CuO/CeO 2 catalyst was characterized in detail. It is demonstrated that the abundant OH species enhanced the CuO x dispersion on CeO 2 , increased the CuO x –CeO 2 interfaces and surface defects, promoted the oxygen activation and mobility, and boosted the NO adsorption and dissociation on CuO/CeO 2 –OH, thus contributing to its superior catalytic activity for both CO oxidation and NO reduction by CO. These results suggest that the OH-rich Ce(OH) x is a superior support for the preparation of highly efficient metal catalysts for different applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Computationally aided, entropy-driven synthesis of highly efficient and durable multi-elemental alloy catalysts

Multi-elemental alloy nanoparticles (MEA-NPs) hold great promise for catalyst discovery in a virtually unlimited compositional space. However, rational and controllable synthesize of these intrinsically complex structures remains a challenge. Here, we report the computationally aided, entropy-driven design and synthesis of highly efficient and durable catalyst MEA-NPs. The computational strategy includes prescreening of millions of compositions, prediction of alloy formation by density functional theory calculations, and examination of structural stability by a hybrid Monte Carlo and molecular dynamics method. Selected compositions can be efficiently and rapidly synthesized at high temperature (e.g., 1500 K, 0.5 s) with excellent thermal stability. We applied these MEA-NPs for catalytic NH 3 decomposition and observed outstanding performance due to the synergistic effect of multi-elemental mixing, their small size, and the alloy phase. We anticipate that the computationally aided rational design and rapid synthesis of MEA-NPs are broadly applicable for various catalytic reactions and will accelerate material discovery.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Tunable CHA/AEI Zeolite Intergrowths with A Priori Biselective Organic Structure‐Directing Agents: Controlling Enrichment and Implications for Selective Catalytic Reduction of NOx

Abstract A novel ab initio methodology based on high‐throughput simulations has permitted designing unique biselective organic structure‐directing agents (OSDAs) that allow the efficient synthesis of CHA/AEI zeolite intergrowth materials with controlled phase compositions. Distinctive local crystallographic ordering of the CHA/AEI intergrowths was revealed at the nanoscale level using integrated differential phase contrast scanning transmission electron microscopy (iDPC STEM). These novel CHA/AEI materials have been tested for the selective catalytic reduction (SCR) of NOx, presenting an outstanding catalytic performance and hydrothermal stability, even surpassing the performance of the well‐established commercial CHA‐type catalyst. This methodology opens the possibility for synthetizing new zeolite intergrowths with more complex structures and unique catalytic properties.

Bello‐Jurado, Estefanía↗
DOE OSTI2022

Tunable CHA/AEI Zeolite Intergrowths with A Priori Biselective Organic Structure‐Directing Agents: Controlling Enrichment and Implications for Selective Catalytic Reduction of NOx

Abstract A novel ab initio methodology based on high‐throughput simulations has permitted designing unique biselective organic structure‐directing agents (OSDAs) that allow the efficient synthesis of CHA/AEI zeolite intergrowth materials with controlled phase compositions. Distinctive local crystallographic ordering of the CHA/AEI intergrowths was revealed at the nanoscale level using integrated differential phase contrast scanning transmission electron microscopy (iDPC STEM). These novel CHA/AEI materials have been tested for the selective catalytic reduction (SCR) of NOx, presenting an outstanding catalytic performance and hydrothermal stability, even surpassing the performance of the well‐established commercial CHA‐type catalyst. This methodology opens the possibility for synthetizing new zeolite intergrowths with more complex structures and unique catalytic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

A Step toward Process Electrification: Microwave-Assisted Co-Gasification of Waste Plastics and Biomass to Produce Clean Energy

Barely 9% of the 353 million metric tons of plastic waste produced worldwide over the last two decades has been recycled, with the majority of it being either landfilled or incinerated. Recycling and upcycling plastic waste is thus essential in mitigating environmental pollution. Gasification is the thermochemical conversion of solid carbon feedstock at high temperatures using a gasifying agent to produce hydrogen-rich syngas. Existing gasification technologies are energy-intensive and require high operating temperatures (>1000 °C), leaving them uncommercial. Microwave heating has sparked attention in a variety of chemical processes due to its specific advantages over traditional heating technologies, such as rapid and selective heating to improve process efficiency. NETL’s research team recently investigated the synergistic advantages of corn stover and mixed plastics in producing hydrogen-rich syngas via microwave heating. As a continuation of the research, this study provides an outlook over the non-catalytic versus catalytic effects of plastic-corn stover gasification via process electrification to enhance H2 production, minimize undesired tar, and improve process efficiency. Our aim is to provide complete electrification of the existing gasification process by using waste plastics as a starting block to produce valuable fuel and support the nation’s net zero goals.

Abedin, Ashraf↗
NASA NTRS1982

Low and medium heating value coal gas catalytic combustor characterization

Catalytic combustion with both low and medium heating value coal gases obtained from an operating gasifier was demonstrated. A practical operating range for efficient operation was determined, and also to identify potential problem areas were identified for consideration during stationary gas turbine engine design. The test rig consists of fuel injectors, a fuel-air premixing section, a catalytic reactor with thermocouple instrumentation and a single point, water cooled sample probe. The test rig included inlet and outlet transition pieces and was designed for installation into an existing test loop.

Schwab, J. A.↗
DOE OSTI2025

Earth-Abundant Manganese Nitride Catalysts for Mild-Condition Ammonia Synthesis

Developing advanced catalytic materials for mild-condition ammonia (NH 3 ) synthesis is essential for improving the energy efficiency of the industrial Haber-Bosch process. Here, in this study, we report a ζ-phase manganese nitride (MnN 0.43 ) catalyst for low-temperature NH 3 synthesis. The as-synthesized MnN 0.43 catalyst is protected by a carbon shell, allowing for the storage and processing of the air-sensitive metal nitride under ambient conditions. After activation in situ, the MnN 0.43 catalyst exhibits high activity for NH 3 synthesis at 250–350 °C, surpassing the conventional noble metal based Ru/MgO catalyst. A combination of kinetic, chemisorption, isotope labeling and computational studies indicate that a nitrogen vacancy-mediated associative mechanism accounts for the catalytic enhancements. Our work highlights the great potential of earth-abundant transition metal nitrides for catalyzing mild-condition NH 3 synthesis.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Zero-Valent Palladium Single-Atoms Catalysts Confined in Black Phosphorus for Efficient Semi-Hydrogenation

Single-atom catalysts (SACs) represent a new frontier in heterogeneous catalysis due to their remarkable catalytic properties and maximized atomic utilization. However, single atoms often bond to the support with polarized electron density and thus exhibit a high valence state, limiting their catalytic scopes in many chemical transformations. In this study, it is demonstrated that 2D black phosphorus (BP) acts as giant phosphorus (P) ligand to confine a high density of single atoms (e.g., Pd 1 , Pt 1 ) via atomic layer deposition. Unlike other 2D materials, BP with relatively low electronegativity and buckled structure favors the strong confinement of robust zero-valent palladium SACs in the vacancy site. Metallic Pd 1 /BP SAC shows a highly selective semi-hydrogenation of phenylacetylene toward styrene, distinct from metallic Pd nanoparticles that facilitate the formation of fully hydrogenated products. Density functional theory calculations reveal that Pd atom forms covalent-like bonding with adjacent P atoms, wherein H atoms tend to adsorb, aiding the dissociative adsorption of H 2 . Zero-valent Pd in the confined space favors a larger energy gain for the synthesis of partially hydrogenated product over the fully hydrogenated one. This work provides a new route toward the synthesis of zero-valent SACs on BP for organic transformations.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Construction of Boron‐ and Nitrogen‐Enriched Nanoporous π‐Conjugated Networks Towards Enhanced Hydrogen Activation

Abstract Boron‐enriched scaffolds have demonstrated unique features and promising performance in the field of catalysis towards the activation of small gas molecules. However, there is still a lack of facile approaches capable of achieving high B doping and abundant porous channels in the targeted catalysts. Herein, construction of boron‐ and nitrogen‐enriched nanoporous π‐conjugated networks (BN‐NCNs) was achieved via a facile ionothermal polymerization procedure with hexaazatriphenylenehexacarbonitrile [HAT(CN) 6 ] sodium borohydride as the starting materials. The as‐produced BN‐NCN scaffolds were featured by high heteroatoms doping (B up to 23 wt. % and N: up to 17 wt. %) and permanent porosity (surface area up to 759 m 2 g −1 mainly contributed by micropores). With the unsaturated bonded B species acting as the active Lewis acid sites and defected N species acting as the active Lewis base sites, those BN‐NCNs delivered attractive catalytic performance towards H 2 activation/dissociation in both gaseous and liquid phase, acting as efficient metal‐free heterogeneous frustrated Lewis pairs (FLPs) catalysts in hydrogenation procedures.

Li, Meijia↗